JP2012149111A - Liquid epoxy resin composition for sealing semiconductor, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured product that has low viscosity, good penetration properties, excellent adhesion to a silicon chip surface etc., and excellent toughness.SOLUTION: A liquid epoxy resin composition for sealing a semiconductor contains (A) a liquid epoxy resin, (B) an aromatic amine-based curing agent, and (C) an inorganic filler comprising an inorganic filler A which is silica having an average particle size of 0.1-3 μm, and an inorganic filler B which is amorphous nanosilica having an average particle size of 5-70 nm, wherein the inorganic filler B is surface treated with a silane coupling agent represented by formulae (1) and/or (2). In formula, n is an integer of 1-5, and m is 1 or 2.

Description

  The present invention provides a cured product with low viscosity, good penetration, excellent adhesion to the surface of the silicon chip, etc., and excellent toughness, and the reflow temperature rises when lead-free solder is used. Even if it does not generate defects, it does not deteriorate even under high-temperature and high-humidity conditions, and a liquid epoxy resin composition for semiconductor encapsulation that can be a sealing material for a semiconductor device that does not cause peeling in a thermal shock test, and this The present invention relates to a semiconductor device sealed with a cured product of the composition.

  Along with the downsizing, weight reduction, and high performance of electrical equipment, the semiconductor mounting method has become the mainstream from the pin insertion type to the surface mounting. One type of bare chip mounting is flip chip (FC) mounting. The FC mounting is a system in which several to tens of thousands of electrodes called bumps having a height of about several μm to about 100 μm are formed on the wiring pattern surface of the LSI chip, and the bumps are bonded to the electrode portions of the substrate. For this reason, the sealing material used for FC sealing protection needs to penetrate into the gap between the substrate and the LSI chip.

  Liquid epoxy resin composition used as a conventional flip-chip underfill material contains an epoxy resin, a curing agent, and an inorganic filler. It is necessary to add a large amount of inorganic filler for the purpose of matching, but if a large amount of inorganic filler is added, the viscosity increases, so that it is difficult to enter the gap between the substrate and the LSI chip, and the productivity becomes very poor. Problems are presented and this improvement is desired.

  In addition, along with the high integration of semiconductor elements, there are cases in which one side of the die size exceeds 10 mm, and the die size is increasing. In a semiconductor device using such a large die, the stress applied to the die and the sealing material increases during solder reflow, and peeling occurs at the interface between the sealing material and the die and the substrate, or the package cracks when mounted on the substrate. These issues have been highlighted.

Furthermore, since lead-containing solder cannot be used in the near future, a number of lead substitute solders have been developed. Since this type of solder has a melting temperature higher than that of lead-containing solder, the reflow temperature is also examined at 260 to 270 ° C., and the conventional liquid epoxy resin composition sealing material is even more defective. Is expected. Thus, when the reflow temperature becomes high, the flip chip type package, which has not had any problems in the past, is cracked during reflow, peeling from the chip interface or the substrate interface occurs, and the number of subsequent thermal cycles If a hundred times or more have passed, a serious problem that a crack occurs in the resin, the substrate, the chip, or the bump portion occurs.
As prior art documents related to the present invention, there are the following.

JP-A-10-158366 JP-A-10-231351 JP 2000-327884 A Japanese Patent Laid-Open No. 2001-055486 JP 2001-055487 A JP 2001-055488 A

  The present invention has been made in view of the above circumstances, and has a low viscosity, good penetration, excellent adhesion to the surface of a silicon chip, particularly a photosensitive polyimide resin or nitride film, and excellent toughness. When lead-free solder is used, no defects occur even when the reflow temperature rises from around 240 ° C to 260-270 ° C. PCT (pressure cooker test, 121 ° C / 2.1 atm) Liquid epoxy resin for semiconductor encapsulation that does not deteriorate even under high temperature and high humidity conditions such as, and can be used as a sealing material for semiconductor devices that does not peel or crack even if it exceeds several hundred cycles in a temperature cycle of -65 ° C./150° C. An object is to provide a composition and a semiconductor device sealed with a cured product of the composition.

As a result of intensive studies to achieve the above object, the present inventors
(A) Liquid epoxy resin,
(B) Aromatic amine-based curing agent: an amount in which the molar ratio of all amino groups in component (B) to all epoxy groups in component (A) is 0.7 to 1.2, and (C) average particles An inorganic filler consisting of an inorganic filler A which is silica having a diameter of 0.1 to 3 μm and an inorganic filler B which is amorphous nanosilica having an average particle diameter of 5 to 70 nm, and the inorganic filler B is specified The content of the inorganic filler B with respect to the whole inorganic filler is surface-treated at a ratio of 3 to 20 parts by mass of the coupling agent with respect to 100 parts by mass of the inorganic filler B. 0.2 to 10% by mass of an inorganic filler: a liquid epoxy resin composition for semiconductor encapsulation containing an amount of 50 to 80% by mass with respect to the total composition comprising the components (A) to (C) The product has a low viscosity, good penetration, Gives a cured product with excellent adhesion to the surface, especially photosensitive polyimide resin and nitride film, and excellent toughness, and reflow temperature rises from around 240 ° C to 260-270 ° C in line with lead-free solder Even if the defect does not occur, it does not deteriorate even under high-temperature and high-humidity conditions such as PCT (121 ° C / 2.1 atm), and even if it exceeds several hundred cycles in a temperature cycle of -65 ° C / 150 ° C, It has been found that it can be a sealing material for a semiconductor device in which cracks do not occur, and the present invention has been made.

（式中、ｎは１〜５の整数、ｍは１又は２である。）
を含有することを特徴とする半導体封止用液状エポキシ樹脂組成物。
請求項２：
カップリング剤が、下記式（２’）で表されるものであることを特徴とする請求項１記載の半導体封止用液状エポキシ樹脂組成物。

請求項３：
（Ｂ）成分が、下記式（３）、（４）、（５）又は（６）で表される芳香族アミン系硬化剤であることを特徴とする請求項１又は２記載の半導体封止用液状エポキシ樹脂組成物。

（式中、Ｒ¹〜Ｒ⁴は水素原子、同一又は異種の炭素数１〜６の一価炭化水素基、ＣＨ₃Ｓ−及びＣ₂Ｈ₅Ｓ−から選ばれる基である。）
請求項４：
請求項１〜３のいずれか１項記載の半導体封止用液状エポキシ樹脂組成物の硬化物で封止された半導体装置。 Accordingly, the present invention provides the following liquid epoxy resin composition for semiconductor encapsulation and a semiconductor device.
Claim 1:
(A) Liquid epoxy resin,
(B) Aromatic amine-based curing agent: an amount in which the molar ratio of all amino groups in component (B) to all epoxy groups in component (A) is 0.7 to 1.2, and (C) average particles An inorganic filler comprising an inorganic filler A which is silica having a diameter of 0.1 to 3 μm and an inorganic filler B which is amorphous nanosilica having an average particle diameter of 5 to 70 nm, wherein the inorganic filler B is The inorganic filler B is surface-treated with a coupling agent represented by the formula (1) and / or (2) at a ratio of 3 to 20 parts by mass of the coupling agent with respect to 100 parts by mass of the inorganic filler B. Inorganic filler having a content of 0.2 to 10% by mass with respect to the entire inorganic filler of the agent B: an amount in which the content of the composition consisting of the components (A) to (C) is 50 to 80% by mass

(In the formula, n is an integer of 1 to 5, and m is 1 or 2.)
A liquid epoxy resin composition for encapsulating a semiconductor, comprising:
Claim 2:
The liquid epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the coupling agent is represented by the following formula (2 ′).

Claim 3:
The component (B) is an aromatic amine-based curing agent represented by the following formula (3), (4), (5), or (6). Liquid epoxy resin composition.

(In the formula, R ^{1 to} R ⁴ are groups selected from a hydrogen atom, the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms, CH ₃ S— and C ₂ H ₅ S—.)
Claim 4:
The semiconductor device sealed with the hardened | cured material of the liquid epoxy resin composition for semiconductor sealing of any one of Claims 1-3.

  According to the present invention, a lead-free solder having a low viscosity, good penetration, a hardened material having excellent adhesion to the surface of a silicon chip, particularly a photosensitive polyimide resin or a nitride film, and excellent toughness is provided. When the reflow temperature is increased from 260 ° C to 260 ° C to 270 ° C from the conventional temperature of about 240 ° C, there is no defect, and it deteriorates even under high temperature and high humidity conditions such as PCT (121 ° C / 2.1 atm). In addition, a liquid epoxy resin composition for semiconductor encapsulation that can be used as a sealing material for a semiconductor device in which peeling and cracking do not occur even when the temperature cycle of −65 ° C./150° C. exceeds several hundred cycles, and a cured product of this composition A semiconductor device sealed with can be provided.

Hereinafter, the present invention will be described in detail.
<Liquid epoxy resin composition>
The liquid epoxy resin composition for semiconductor encapsulation of the present invention comprises the above components (A) to (C), and optionally contains other optional components such as a low stress agent. Also good. A solvent may be used.
Hereinafter, the components (A) to (C) and other optional components will be described in detail.

[Component (A)]
The liquid epoxy resin which is the component (A) has an epoxy group having three or less functional groups in one molecule and may be liquid at room temperature (20 to 30 ° C.), and all conventionally known ones are used. be able to. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol type epoxy resin such as bisphenol AD type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, novolak type epoxy resin such as cresol novolac type epoxy resin, biphenyl Type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin, dicyclopentadiene type epoxy resin and the like.

  In particular, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, bisphenol type epoxy resins, naphthalene type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, etc. that have excellent heat resistance and moisture resistance The novolak type epoxy resin is preferable. Among these, an epoxy resin which is liquid at normal temperature (20 to 30 ° C., particularly 25 ° C.) and has a viscosity by a rotational viscometer of 200 Pa · s or less, particularly 50 Pa · s or less is preferable.

Further, the liquid epoxy resin may contain an epoxy resin represented by the following structural formulas (7) and (8) within a range that does not affect the invasion property.

In said formula (8), R < ⁵ > is a hydrogen atom or a C1-C20, Preferably it is 1-10, More preferably, it is a 1-3 monovalent hydrocarbon group, As a monovalent hydrocarbon group, methyl is Group, alkyl group such as ethyl group, propyl group and isopropyl group, and alkenyl group such as vinyl group and allyl group. X is an integer of 1 to 4, particularly 1 or 2.

  When the epoxy resin represented by the above formula (7) is blended, the blending amount is recommended to be 10% by mass or more, more preferably 25% by mass or more, and still more preferably 50% by mass or more in the total epoxy resin. The If it is less than 10% by mass, the heat resistance may be lowered or the viscosity may be increased. The upper limit may be 100% by mass.

  Examples of the epoxy resin represented by the above formula (7) include jER630LSD manufactured by Mitsubishi Chemical Corporation.

  When the epoxy resin represented by the above formula (8) is blended, it is recommended that the blending amount is 25% by mass or more, more preferably 50% by mass or more, further preferably 75% by mass or more in the total epoxy resin. The If it is less than 25% by mass, the viscosity of the composition may increase or the heat resistance of the cured product may decrease. The upper limit may be 100% by mass.

  Examples of the epoxy resin represented by the above formula (8) include RE600NM manufactured by Nippon Kayaku Co., Ltd.

The epoxy resin contains a small amount of epichlorohydrin-derived chlorine used in the synthesis process, and the total chlorine content in the liquid epoxy resin is 1,500 ppm or less, preferably 1,000 ppm or less. preferable. Moreover, it is preferable that the extraction water chlorine in 20 hours in the 50% epoxy resin density | concentration at 100 degreeC is 10 ppm or less. If the total chlorine content exceeds 1,500 ppm or the extracted water chlorine exceeds 10 ppm, the reliability of the semiconductor element, particularly the moisture resistance, may be adversely affected.
The epoxy resins described above can be used singly or in combination of two or more.

（式中、Ｒ¹〜Ｒ⁴は水素原子、同一又は異種の炭素数１〜６の一価炭化水素基、ＣＨ₃Ｓ−及びＣ₂Ｈ₅Ｓ−から選ばれる基である。） [(B) component]
The aromatic amine curing agent (B) is a curing agent of the above component (A), which is an amine compound having an aromatic ring excellent in heat resistance and storage stability, and preferably the following formula (3 ), (4), (5) or (6).

(In the formula, R ^{1 to} R ⁴ are groups selected from a hydrogen atom, the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms, CH ₃ S— and C ₂ H ₅ S—.)

Among the aromatic amine curing agents represented by the above formula (3), (4), (5) or (6), for example, 3,3′-diethyl-4,4′-diaminophenylmethane, 3, Aromatic diaminodiphenylmethane compounds such as 3 ′, 5,5′-tetramethyl-4,4′-diaminophenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminophenylmethane, 4-diaminotoluene, 1,4-diaminobenzene, 1,3-diaminobenzene and the like are preferably used.
These can be used individually by 1 type or in combination of 2 or more types.

  Among the above aromatic amine curing agents, those which are liquid at normal temperature (20 to 30 ° C.) can be blended as they are, but if they are blended as they are, the viscosity of the resin increases and the workability is extremely poor. Therefore, it is preferable to melt and mix with the liquid epoxy resin in advance, and it is desirable to melt and mix at a specific blending ratio described later at a temperature range of 70 to 150 ° C. for 1 to 2 hours. If the mixing temperature is less than 70 ° C., the aromatic amine curing agent may not be sufficiently compatible, and if the mixing temperature exceeds 150 ° C., it may react with the liquid epoxy resin and increase the viscosity. Also, if the mixing time is less than 1 hour, the aromatic amine curing agent is not sufficiently compatible and may increase the viscosity, and if it exceeds 2 hours, it may react with the liquid epoxy resin and increase the viscosity. is there.

  The blending amount of the aromatic amine curing agent is such that the molar ratio of all amino groups in the aromatic amine curing agent to all epoxy groups in the component (A) is 0.7 to 1.2, preferably 0. 0.7 to 1.1, more preferably 0.85 to 1.05. When the blending molar ratio is less than 0.7, unreacted epoxy groups remain, and the glass transition temperature may be lowered or the adhesion may be lowered. On the other hand, if the ratio exceeds 1.2, the cured product becomes hard and brittle, and cracks may occur during reflow or temperature cycling.

[Component (C)]
The inorganic filler as component (C) is an inorganic filler composed of inorganic filler A which is silica having an average particle diameter of 0.1 to 3 μm and inorganic filler B which is amorphous nanosilica having an average particle diameter of 5 to 70 nm. It is a filler, and the inorganic filler B is a coupling agent represented by the formula (1) and / or (2) described later, and the coupling agent is 3 to 20 masses per 100 mass parts of the inorganic filler B. It is an inorganic filler that is surface-treated at a ratio of parts and that the content of the inorganic filler B with respect to the entire inorganic filler is 0.2 to 10% by mass.

  Such inorganic fillers A and B are composed of spherical silica, and the average particle size can be measured by a known centrifugal sedimentation method, laser diffraction method, dynamic light scattering method, or the like. However, the inorganic filler A is preferably a laser diffraction method that allows simple and wide-ranging measurement of particle diameters, and the inorganic filler B is preferably a dynamic light scattering method with high submicron accuracy.

  The inorganic filler A needs to have an average particle size of 0.1 to 3 μm, preferably 0.3 to 2 μm. If the average particle size exceeds 3 μm, the cross-sectional area of penetration is reduced, affecting the penetration, and the filler settles during penetration and curing, causing a gradient in the thermal expansion coefficient between the chip side and the substrate side, Reliability against thermal shock is reduced. On the other hand, when the average particle size is less than 1 μm, the viscosity becomes high.

Inorganic filler A may be blended in advance with a surface treatment with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to increase the bond strength between the resin and the inorganic filler. As such a coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N Silane cups such as amino silanes such as -β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and mercaptosilane such as γ-mercaptosilane It is preferable to use a ring agent.
In addition, about the compounding quantity of the coupling agent used for surface treatment, and a surface treatment method, a well-known method can be used and it does not restrict | limit in particular.

  The inorganic filler B is amorphous nanosilica particles, and it is necessary to control the average particle size to 5 to 50 nm, preferably 10 to 50 nm. By subjecting the inorganic filler B having such an average particle diameter to a surface treatment with a coupling agent described later and using the inorganic filler B in combination with the inorganic filler A at a specific ratio, the thin film penetration property can be further improved.

  Such amorphous nanosilica particles form a chemical flame with a burner in an oxygen-containing atmosphere as described in, for example, Japanese Examined Patent Publication No. 1-55201, and metal silicon is dust clouded in the chemical flame. Can be synthesized to form an explosion and cause an explosion.

（式中、ｎは１〜５の整数、ｍは１又は２である。） As a silane coupling agent for surface-treating amorphous nanosilica, either one or both of those represented by the following formula (1) or (2) are used, and particularly represented by the following formula (2 ′). Those are preferably used.

(In the formula, n is an integer of 1 to 5, and m is 1 or 2.)

  As a silane coupling agent like the said Formula (1) or (2), KBM103, KBM503, KBE503 (made by Shin-Etsu Chemical Co., Ltd.) etc. are mentioned, for example.

  Representative coupling agents other than those represented by the above formula (1), for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxy silane such as ethyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, aminosilane such as N-phenyl-γ-aminopropyltrimethoxysilane, γ -When surface treatment of the amorphous nanosilica particles is performed with a silane coupling agent such as mercaptosilane such as mercaptosilane, the amorphous nanosilica particles may be aggregated or generated and cannot be dispersed in the liquid epoxy resin composition. is there.

When surface-treating the inorganic filler B with the coupling agent represented by the above formula (1), 3 to 20 parts by mass, more preferably 5 to 5 parts by mass of the coupling agent with respect to 100 parts by mass of the inorganic filler B. Surface treatment can be performed with a blending amount of 15 parts by mass. If the blending amount is less than 3 parts by mass, the strength may decrease. On the other hand, if it exceeds 20 parts by mass, the strength may decrease.
In addition, about the compounding quantity of the said coupling agent used for surface treatment, and a surface treatment method, a well-known method can be used and it does not restrict | limit in particular.

  Further, the content of the inorganic filler B with respect to the entire inorganic filler needs to be controlled to 0.2 to 10% by mass, more preferably 0.5 to 5% by mass, and this content is controlled within the above range. By doing so, the viscosity of the liquid epoxy resin composition can be reduced, and the narrow gap can be favorably penetrated. The reason is not clear, but in the composition having a large proportion of the organic resin, the influence of the fine powder on the matrix is included in the fluidity of the organic resin, but the total content of the inorganic filler is relative to the organic resin. It is considered that the behavior of the fluidity of the organic resin in the gap varies depending on the amount of the nano-sized inorganic filler B, and the effect is exerted as the driving force.

  The content of the inorganic filler as the component (C) is 50 to 80% by mass, more preferably 60 to 75% by mass, based on the entire composition composed of the components (A) to (C). . When the content is less than 50% by mass, the coefficient of expansion is large and the occurrence of cracks is induced in the cooling test, and when it exceeds 80% by mass, the viscosity increases and the penetration of the thin film is reduced.

  The semiconductor device targeted by the present invention is preferably a semiconductor device having a gap size range of about 10 to 200 μm, particularly a flip chip type semiconductor device, and a Philip chip type semiconductor device having a die size of more than 10 mm. In this case, in order to achieve both improved penetration of the underfill material and low linear expansion, the average particle size is about 1/10 or less with respect to the flip chip gap width (gap between the substrate and the semiconductor chip). It is preferable to use an inorganic filler having a diameter of 1/2 or less.

[Other ingredients]
The liquid epoxy resin composition for semiconductor encapsulation of the present invention can further contain various additives as necessary. For example, thermoplastic resin, thermoplastic elastomer, organic synthetic rubber, silicone-based low stress agent (for example, block copolymer of epoxy resin such as novolak type epoxy resin and organopolysiloxane), carnauba wax, higher fatty acid In addition, waxes such as synthetic waxes, colorants such as carbon black, additives such as halogen trap agents, and solvents can be added and blended.
As the solvent, methyl ethyl ketone, carbitol acetate, or the like can be used.

<Method for producing composition>
The manufacturing method of the liquid epoxy resin composition for semiconductor encapsulation is the above-mentioned components (A) to (C), and other components at the same time or separately, if necessary, stirring, dissolving, mixing while adding heat treatment as necessary. It can be obtained by dispersing. The apparatus for mixing, stirring, dispersing and the like is not particularly limited, and a lykai machine, a three roll, a ball mill, a planetary mixer, a bead mill and the like equipped with a stirring and heating device can be used. Moreover, you may use combining these apparatuses suitably.

<Method of curing composition>
The curing method of the liquid epoxy resin composition for semiconductor encapsulation may be a known method, but preferably 100 to 120 ° C. for 0.5 hour or more, particularly 0.5 to 2 hours, and then 130 to 130 ° C. Heat oven curing is performed under the conditions of 250 ° C. and 0.5 hours or more, particularly 0.5 to 5 hours. When heating at 100 to 120 ° C. is less than 0.5 hour, voids may occur after curing. Further, if the heating at 130 to 250 ° C. is less than 0.5 hour, sufficient cured product characteristics may not be obtained.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to a following example.

（Ｂ）アミン系硬化剤
・４，４’−ジアミノ−３，３’−ジエチルジフェニルメタン（日本化薬（株）製）
（Ｃ）無機充填剤
表１に基づき、球状シリカ粒子を表面処理することにより、各種無機充填剤を得た。
なお、表１中のカップリング剤の配合量は球状シリカ粒子１００質量部に対するものである。

・カップリング剤：ＫＢＭ４０３、３−グリシドキシプロピルトリメトキシシラン（信越化学工業（株）製）
・カップリング剤：ＫＢＭ５７３、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン（信越化学工業（株）製）
・カップリング剤：ＫＢＭ１０３、フェニルトリメトキシシラン（信越化学工業（株）製）
・カップリング剤：ＫＢＭ５０３、３−メタクリロキシプロピルトリメトキシシラン（信越化学工業（株）製）
（Ｄ）その他の成分
・カップリング剤：ＫＢＭ４０３、３−グリシドキシプロピルトリメトキシシラン（信越化学工業（株）製）
・カーボンブラック：デンカブラック（電気化学工業（株）製）
・触媒：ＤＢＵ（サンアプロ化成（株）製）
・溶剤：ＥＤＧＡＣ（ダイセル化学（株）製） [Examples 1-8, Comparative Examples 1-5]
Various epoxy resin compositions were obtained by blending a liquid epoxy resin, a curing agent, an inorganic filler and other components based on Tables 2 and 3 and kneading them uniformly with three rolls.
[Materials used]
(A) Liquid epoxy resin / bisphenol F type epoxy resin: YDF8170 (manufactured by Toto Kasei Co., Ltd.)
-Epoxy resin represented by the following formula (7): jER630LSD (manufactured by Mitsubishi Chemical Corporation)

(B) Amine-based curing agent • 4,4′-diamino-3,3′-diethyldiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.)
(C) Inorganic filler Based on Table 1, various inorganic fillers were obtained by surface-treating spherical silica particles.
In addition, the compounding quantity of the coupling agent of Table 1 is with respect to 100 mass parts of spherical silica particles.

Coupling agent: KBM403, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
Coupling agent: KBM573, N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
Coupling agent: KBM103, phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
Coupling agent: KBM503, 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
(D) Other components and coupling agents: KBM403, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Carbon black: Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd.)
・ Catalyst: DBU (manufactured by Sun Apro Chemical Co., Ltd.)
・ Solvent: EDGAC (manufactured by Daicel Chemical Industries)

〔Evaluation methods〕
(1) Viscosity The viscosity at 25 ° C. was measured at a rotation speed of 4 rpm using a BH type rotational viscometer.

(2) Tg (glass transition temperature), CTE1 (expansion coefficient), CTE2 (expansion coefficient)
Various compositions were cured at 120 ° C./0.5 hours + 165 ° C./3 hours to prepare a cured product test piece of 5 mm × 5 mm × 15 mm. Using this test piece, Tg when the temperature was raised at a rate of 5 ° C. per minute by TMA (thermomechanical analyzer) was measured. Moreover, the expansion coefficient in the following temperature range was measured. The temperature range of CTE1 is 50 to 80 ° C, and the temperature range of CTE2 is 200 to 230 ° C.

(3) Toughness value K _1c
Various compositions were cured at 120 ° C./0.5 hours + 165 ° C./3 hours, and the toughness value K _1c at room temperature was measured for the obtained cured product based on ASTM # D5045.

(4) Adhesion test Each resin composition was injected into a truncated cone-shaped polytetrafluoroethylene mold having a diameter of 2 mm on the upper surface, a diameter of 5 mm on the lower surface, and a height of 3 mm, and a polyimide (PI) film was coated thereon. A silicon chip or copper plate was placed and cured at 150 ° C. for 3 hours. After curing, the test piece obtained by removing the polytetrafluoroethylene mold was pushed at a constant speed (1 mm / sec) to measure the shear adhesive force, and set it as the initial value. Furthermore, after holding the cured test piece in a pressure cooker tester (121 ° C./2.1 atm) for 72 hours, the adhesive strength was measured in the same manner. In any case, the number of test pieces was five, and the average value was expressed as adhesive strength. In Table 2, “0” indicates peeling.

(5) Void test 30 mm × 30 mm FR-4 substrate, 10 mm × 10 mm silicon chip coated with polyimide (PI) film is placed in the gap of the flip chip type semiconductor device installed so that the gap size is about 50 μm. Each resin composition was dropped and infiltrated, and after curing at 150 ° C. for 3 hours, the presence or absence of voids was confirmed by C-SAM (manufactured by SONIX).

(6) Thermal shock test The test semiconductor device obtained by the above method was placed in a condition of 30 ° C./65% RH for 192 hours and passed through an IR reflow furnace set at a maximum temperature of 265 ° C. five times. The ratio of chips in which cracks were observed in the same manner as described above for cracks after 250, 500, 750, 1,000, and 1,250 cycles, with 30 minutes at -65 ° C and 30 minutes at 150 ° C as one cycle. (%) Was calculated.

  According to the present invention, a lead-free solder having a low viscosity, good penetration, a hardened material having excellent adhesion to the surface of a silicon chip, particularly a photosensitive polyimide resin or a nitride film, and excellent toughness is provided. For semiconductor sealing that can be used as a sealing material for semiconductor devices that does not cause defects even when the reflow temperature rises, does not deteriorate even under high temperature and high humidity conditions, and does not peel off in thermal shock tests Since a semiconductor device sealed with a liquid epoxy resin composition and a cured product of this composition can be provided, its industrial utility value is high.

（式中、ｎは１〜５の整数、ｍは１又は２である。）
を含有することを特徴とする半導体封止用液状エポキシ樹脂組成物。
請求項２：
カップリング剤が、下記式（２’）で表されるものであることを特徴とする請求項１記載の半導体封止用液状エポキシ樹脂組成物。

請求項３：
（Ｂ）成分が、下記式（３）、（４）、（５）又は（６）で表される芳香族アミン系硬化剤であることを特徴とする請求項１又は２記載の半導体封止用液状エポキシ樹脂組成物。

（式中、Ｒ¹〜Ｒ⁴は水素原子、同一又は異種の炭素数１〜６の一価炭化水素基、ＣＨ₃Ｓ−及びＣ₂Ｈ₅Ｓ−から選ばれる基である。）
請求項４：
請求項１〜３のいずれか１項記載の半導体封止用液状エポキシ樹脂組成物の硬化物で封止された半導体装置。 Accordingly, the present invention provides the following liquid epoxy resin composition for semiconductor encapsulation and a semiconductor device.
Claim 1:
(A) Liquid epoxy resin,
(B) Aromatic amine-based curing agent: an amount in which the molar ratio of all amino groups in component (B) to all epoxy groups in component (A) is 0.7 to 1.2, and (C) average particles An inorganic filler comprising an inorganic filler A which is silica having a diameter of 0.1 to 3 μm and an inorganic filler B which is amorphous nanosilica having an average particle diameter of 5 to 70 nm, wherein the inorganic filler B is The inorganic filler B is surface-treated with a coupling agent represented by the formula (1) and / or (2) at a ratio of 3 to 20 parts by mass of the coupling agent with respect to 100 parts by mass of the inorganic filler B. Inorganic filler having a content of 0.2 to 10% by mass with respect to the entire inorganic filler of the agent B: an amount in which the content of the composition consisting of the components (A) to (C) is 50 to 80% by mass

(In the formula, n is an integer of 1 to 5, and m is 1 or 2.)
A liquid epoxy resin composition for encapsulating a semiconductor, comprising:
Claim 2:
The liquid epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the coupling agent is represented by the following formula (2 ′).

Claim 3:
The component (B) is an aromatic amine-based curing agent represented by the following formula (3), (4), (5), or (6). Liquid epoxy resin composition.

(In the formula, R ^{1 to} R ⁴ are groups selected from a hydrogen atom, the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms, CH ₃ S— and C ₂ H ₅ S—.)
Claim 4:
The semiconductor device sealed with the hardened | cured material of the liquid epoxy resin composition for semiconductor sealing of any one of Claims 1-3.

Representative coupling agents other than those represented by the above formulas (1) and (2) , for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3, Epoxy silanes such as 4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. When the amorphous nanosilica particles are surface-treated with a silane coupling agent such as mercaptosilane such as aminosilane or γ-mercaptosilane, the amorphous nanosilica particles are aggregated or generated and dispersed in the liquid epoxy resin composition. It may not be possible.

When surface-treating the inorganic filler B with the coupling agent represented by the above formula (1) or (2) , 3 to 20 parts by mass of the coupling agent with respect to 100 parts by mass of the inorganic filler B Preferably, the surface treatment can be performed at a blending amount of 5 to 15 parts by mass. If the blending amount is less than 3 parts by mass, the strength may decrease. On the other hand, if it exceeds 20 parts by mass, the strength may decrease.
In addition, about the compounding quantity of the said coupling agent used for surface treatment, and a surface treatment method, a well-known method can be used and it does not restrict | limit in particular.

Claims (4)

(A) Liquid epoxy resin,
(B) Aromatic amine-based curing agent: an amount in which the molar ratio of all amino groups in component (B) to all epoxy groups in component (A) is 0.7 to 1.2, and (C) average particles An inorganic filler comprising an inorganic filler A which is silica having a diameter of 0.1 to 3 μm and an inorganic filler B which is amorphous nanosilica having an average particle diameter of 5 to 70 nm, wherein the inorganic filler B is The inorganic filler B is surface-treated with a coupling agent represented by the formula (1) and / or (2) at a ratio of 3 to 20 parts by mass of the coupling agent with respect to 100 parts by mass of the inorganic filler B. Inorganic filler having a content of 0.2 to 10% by mass with respect to the entire inorganic filler of the agent B: an amount in which the content of the composition consisting of the components (A) to (C) is 50 to 80% by mass

(In the formula, n is an integer of 1 to 5, and m is 1 or 2.)
A liquid epoxy resin composition for encapsulating a semiconductor, comprising: The liquid epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the coupling agent is represented by the following formula (2 ′).

The component (B) is an aromatic amine-based curing agent represented by the following formula (3), (4), (5), or (6). Liquid epoxy resin composition.

(In the formula, R ^{1 to} R ⁴ are groups selected from a hydrogen atom, the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms, CH ₃ S— and C ₂ H ₅ S—.)   The semiconductor device sealed with the hardened | cured material of the liquid epoxy resin composition for semiconductor sealing of any one of Claims 1-3.